The biodegradation of tar-rich coal in the Ordos Basin was carried out by Bacillus licheniformis (B. licheniformis) under actions of four kinds of surfactants, namely, a biological surfactant (Rh), a nonionic surfactant (Triton X-100), an anionic surfactant (LAS), and a cationic surfactant (DTAB). The biodegradation rates under the actions of Triton X-100, LAS, Rh, DTAB, and the control group (without surfactant) were 59.8%, 54.3%, 51.6%, 17.3%, and 43.5%, respectively. The biodegradation mechanism was studied by examining the influences of surfactants on coal samples, bacteria, and degradation products in the degradation process. The results demonstrated that Rh, Triton X-100, and LAS could promote bacterial growth, while DTAB had the opposite effect. Four surfactants all increased the cell surface hydrophobicity (CSH) of B. licheniformis, and Triton X-100 demonstrated the most significant promotion of CSH. The order of improvement in microbial cell permeability by surfactants was DTAB > TritonX-100 > LAS > Rh > control group. In the presence of four surfactants, Triton X-100 exhibited the best hydrophilicity improvement for oxidized coal. Overall, among the four surfactants, Triton X-100 ranked first in enhancing the CSH of bacteria and the hydrophilicity of oxidized coal and second in improving microbial cell permeability; thus, Triton X-100 was the most suitable surfactant for promoting B. licheniformis's biodegradation of tar-rich coal. The GC-MS showed that, after the action of Triton X-100, the amount of the identified degradation compounds in the toluene extract of the liquid product decreased by 16 compared to the control group, the amount of dichloromethane extract decreased by 6, and the amount of ethyl acetate extract increased by 6. Simultaneously, the contents of alkanes in the extracts of toluene and dichloromethane decreased, lipids increased, and ethyl acetate extract exhibited little change. The FTIR analysis of the coal sample suggested that, under the action of Triton X-100, compared to oxidized coal, the Har/H and A(CH2)/A(CH3) of the remaining coal decreased by 0.07 and 1.38, respectively, indicating that Triton X-100 enhanced the degradation of aromatic and aliphatic structures of oxidized coal. Therefore, adding a suitable surfactant can promote the biodegradation of tar-rich coal and enrich its degradation product.